DE4232417A1 - Substituted thienylsulfonylureas - Google Patents

Description

The invention relates to new substituted thienylsulfonylureas, processes and new intermediates for their manufacture and their use as herbicides.

It is already known that certain substituted thienylsulfonylureas, such as. B. N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N '- (2-methoxycarbonylthie-n-3-yl-sulfo nyl) urea (thifensulfuron-methyl), show strong herbicidal activity (cf. EP- A 30142). The effect of these compounds - especially their tolerance compared to crops - is not always entirely satisfactory.

There have now been the new substituted thienylsulfonylureas of the general Formula (I)

in which
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X and Y are the same or different and each represents hydrogen, hydroxy, amino, cyano, halogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ -Cydoalkyl, C ₁ -C ₄ - haloalkyl, C ₁ -C ₄ - alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - haloalkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ - C ₄ alkylamino or di (C ₁ -C ₄ alkyl) amino and
Z represents nitrogen, a CH group or a C-halogen group,
as well as salts of compounds of formula (I) found.

The new substituted thienylsulfonylureas of the general formula are obtained (I) if one

• a) thiophene sulfonamides of the general formula (II) in which
  R ^{1 has} the meaning given above,
  with chloroformic acid esters of the general formula (III) CI-CO-O-R³ (III) in which
  R ^{3 represents} C ₁ -C ₄ alkyl, phenyl or benzyl,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and the urethanes (carbamates) of the general formula (IV) formed in which
  R ¹ and R ^{3 have} the meaning given above, - optionally without intermediate insulation -
  with azines of the general formula (V) in which
  R ² , X, Y and Z have the meaning given above,
  if appropriate in the presence of a reaction auxiliary, or if one
• b) thienylsulfonyl isocyanates of the general formula (VI) in which
  R ^{1 has} the meaning given above,
  with azines of the general formula (V) in which
  R ² , X, Y and Z have the meaning given above,
  if appropriate in the presence of a diluent.

The new substituted thienylsulfonylureas of the general formula (I) drawing are characterized by strong and selective effectiveness.

Surprisingly, the new compounds of formula (I) show very good ones Compatibility with crops, such as. B. wheat, much stronger we against some problem weeds than those known from the prior art Thienylsulfonylureas.

The invention preferably relates to compounds of the formula (I) in which
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X for hydrogen, hydroxy, amino, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, trifluoromethyl, methoxy methyl, ethoxymethyl, methoxyethyl , Ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chloroethoxy, fluoroethoxy, dichloroethoxy, difluoroethoxy, trichloroethoxy, trifluoroethoxy, chlorodifluoroethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, nio or io-thio, n- Ethylamino, n- or i-propylamino, dimethylamino or diethylamino,
Y represents hydrogen, hydroxy, amino, cyano, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino and
Z represents nitrogen or a CH group.

The invention further relates preferably to salts obtained from compounds of formula (I) and bases, such as. B. sodium, potassium or calcium hydroxide, hydride, amide or carbonate, sodium or potassium C ₁ -C ₄ alkanolates, ammonia, C ₁ -C ₄ alkyl amines, di (C ₁ -C ₄ alkyl) amines or tri- (C ₁ -C ₄ alkyl) amines.

The invention relates in particular to compounds of the formula (I) in which
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X represents methyl, methoxy or methylthio,
Y represents hydrogen, methyl, methoxy or methylthio and
Z represents nitrogen or a CH group.

The general or priority ranges listed above nitions or explanations apply to the end products and to the initial and Intermediates accordingly. These residual definitions can be among themselves, that is can also be combined as desired between the respective preferred areas.

For example, 2-ethoxycarbonyl-thio is used for process variant (a) phen-3-sulfonamide and chloroformic acid methyl ester and 2-amino-4,6-dimethoxy pyrimidine as starting materials, the reaction can be carried out by the following Formula scheme are outlined:

For example, 2-propoxycarbonyl-thio is used for process variant (b) phen-3-yl-sulfonyl isocyanate and 2-methylamino-4,6-dimethoxy-s-triazine as Aus materials, the course of the reaction can be outlined using the following formula become:

The starting materials in the production process (a) according to the invention using thiophene sulfonamides - 2-ethoxycarbonyl-thiophene-3-sulfonamide and 2-propoxycarbonyl-thiophene-3-sulfonamide - are not yet known from the literature and as new substances are the subject of this patent application.

The new thiophenesulfonamides of the formula (II) are obtained if they are corresponding Thiophene sulfonic acid chlorides of the general formula (VII)

in which
R ^{1 has} the meaning given above,
with ammonia, optionally in the presence of a diluent, such as. B. Me methylene chloride, at temperatures between -30 ° C and + 50 ° C (see. Her position examples).

Of the thiophene sulfonic acid chlorides of the formula (VII) is 2-ethoxycarbonyl-thio phen-3-sulfonic acid chloride already known (cf. ES-P 556919 - cited in Chem. Ab stracts 109: 93034w).

In contrast, 2-propoxycarbonyl-thiophene-3-sulfonic acid chloride is not yet out of the Lite known and is the subject of the present patent as a new substance report.  

The new 2-propoxycarbonyl-thiophene-3-sulfonic acid chloride is obtained if 3- Amino-thiophene-2-carboxylic acid propyl ester with sodium nitrite in the presence of salt acid at temperatures between -10 ° C and + 10 ° C and then with sulfur dioxide in Presence of a copper catalyst, such as. B. copper (I) chloride, and in the presence a diluent, such as. B. acetic acid, at temperatures between 10 ° C and 50 ° C (see the manufacturing examples).

The 3-amino-thiophene-2-carboxylic acid propyl ester required as a preliminary product is still not known from the literature and as a new substance is also the subject of present patent application.

The new 3-amino-thiophene-2-carboxylic acid propyl ester is obtained if thio propyl glycolate with 2-chloroacrylonitrile in the presence of an acid acceptor, such as As sodium propanolate, and in the presence of a diluent, such as. B. Propanol, at temperatures between 0 ° C and 100 ° C (cf. the manufacturing examples).

The process (a) according to the invention for the preparation of compounds of Formula (I) are further chloroformic acid esters to be used as starting materials generally defined by formula (III).

In formula (III), R ^{3 is} preferably methyl, ethyl, phenyl or benzyl, especially phenyl.

The starting materials of the formula (III) are known synthetic chemicals.

The urethanes (carba mate) of formula (IV) are not yet known from the literature and are new Substances are also the subject of this patent application.

In formula (IV), R ¹ and R ³ preferably or in particular have those meanings which have already been described above in connection with the description of the compounds of the formula (I) or (III) preferably or as particularly preferred for R ¹ and R ^{3 were} specified.

Formula (V) provides a general definition of the azines to be used further as starting materials in process (a) according to the invention for the preparation of compounds of formula (I).
In formula (V), R ² , X, Y and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention, preferably or as particularly preferred for R ² , X , Y and Z were specified.

The starting materials of the formula (V) are known and / or can be per se known processes can be prepared (cf. US-P 4299960; EP-A 121082; EP-A 125205; EP-A 126711; EP-A 152378; EP-A 158594).

Process (a) according to the invention for the preparation of the new compounds of Formula (I) is preferably carried out using diluents guided. Practically all inert organic solvents are used as diluents means in question. These preferably include aliphatic and aromatic ones halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, Petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, Chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as Diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, Tetrahy drofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and Me thyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as. B. Acetonitrile and propionitrile, amides such as e.g. B. dimethylformamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexa methylphosphoric triamide.

All of them can be used as acid acceptors in process (a) according to the invention Acid binders which can usually be used for such reactions are used become. Alkali metal and alkaline earth metal hydrides, such as Lithium, sodium, potassium and calcium hydride, alkali metal and alkaline earth metal hydroxides, such as lithium, sodium, potassium and calcium hydroxide, alkali metal and Alkaline earth metal carbonates and bicarbonates, such as sodium and potassium carbo nate or bicarbonate and calcium carbonate, alkali metal acetates such as Na  trium and potassium acetate, alkali metal alcoholates, such as sodium and potassium methylate, -ethylate, -propylate, -isopropylate, -butylate, -isobutylate and tert-butoxide, also basic Nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributyl amine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohe xylamine, N, N-dimethylbenzylamine, N, N-dimethyl-aniline, pyridine, 2-methyl, 3-Me ethyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 2-ethyl, 4-ethyl and 5-ethyl-2- methyl pyridine, 1,5-diazabicylo [4,3,0] -non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] - undec-7-ene (DBU) and 1,4-diazabicyclo [2,2,2] octane (DABCO).

The second implementation phase of the method according to the invention, i. H. the implementation with the azines of formula (V), is preferably in the presence of a reaction tools carried out. Acid is preferably used as the reaction auxiliary ren used, especially protic acids, such as sulfuric acid, methanesulfonic acid, Benzenesulfonic acid and p-toluenesulfonic acid.

The reaction temperatures in process (a) according to the invention can be in can be varied over a wide range. Generally one works at Tempera structures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Process (a) according to the invention is generally carried out under atmospheric pressure guided. However, it is also possible to increase or decrease pressure work.

To carry out process (a) according to the invention, they are required in each case th raw materials generally used in approximately equimolar amounts. It However, it is also possible to use one or more of the components used in each case to use a larger excess.

Preferably the thiophene sulfonamides of the formula (II) with chlorine reacted formic acid esters of formula (III) and then the ure formed thane of formula (IV) without intermediate isolation with the azines of formula (V) for Implemented. The reaction mixture is then generally increased Temperature stirred until the end of the reaction and then in the usual way worked up (see the manufacturing examples).  

The ver in the manufacturing process (b) according to the invention as starting materials turning thienylsulfonyl isocyanates - 2-ethoxycarbonyl-thien-3-ylsulfonyl isocyanate and 2-propoxycarbonyl-thien-3-ylsulfonyl isocyanate - are not yet from the literature are known and are the subject of the present patent application as new substances.

The new thienylsulfonyl isocyanates of the formula (VI) are obtained if one corresponds thiophene sulfonamides of the general formula (II)

in which
R ^{1 has} the meaning given above,
with phosgene, preferably in the presence of an alkyl isocyanate, such as. B. Butylisocya nat, in the presence of a reaction auxiliary, such as. B. diazabicyclo [2.2.2] octane, and in the presence of a diluent, such as. B. xylene, at temperatures between 100 ° C and 150 ° C and after the end of the reaction, the volatile components are distilled off under reduced pressure.

Process (b) according to the invention is further carried out using azines general formula (V) performed. The same information applies here that above in the description of the starting materials for the process according to the invention (a) were made with respect to the azines of formula (V).

Process (b) according to the invention is preferably carried out using a Diluent carried out. There are preferably those organizations nical solvents that are considered above for process (a) according to the invention were specified.

To carry out process (b) according to the invention, the respective be necessary starting materials are generally used in approximately equimolar amounts puts. However, it is also possible to use one of the two components used in each case  to use in a larger excess. The reactions are general performed in a suitable diluent, and the reaction mixture is stirred for several hours at the required temperature. The workup takes place in the process (b) according to the invention in each case by customary methods (see the manufacturing examples).

From the compounds of the general formula (I) according to the invention, if necessary salts are produced. Such salts are obtained in a simple manner usual salt formation methods, for example by dissolving or dispersing one Compound of formula (I) in a suitable diluent, such as. B. Methy Lenchlorid, acetone, tert-butyl methyl ether or toluene, and addition of a suitable Base. The salts can then - if necessary after prolonged stirring - by Ein narrow or suction isolated.

The active compounds according to the invention can be used as defoliants, desiccants, herb kills Means and especially used as a weed killer. Under Weeds in the broadest sense are all plants that grow in places, where they are undesirable. Whether the substances according to the invention as total or selective Herbicides act essentially depends on the amount applied.

The active compounds according to the invention can, for. B. used in the following plants become:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthi um, convolvulus, ipomoea, polygonum, sesbania, ambrosia, cirsium, carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pi sum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sor  ghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these Genres limited, but extends in the same way to other plants Zen.

The compounds are suitable depending on the concentration Total weed control e.g. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to weeds control in permanent crops, e.g. B. forest, ornamental wood, fruit, wine, citrus, nut, Banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plant on ornamental and sports turf and pastures and for selective weed beds fighting in annual crops.

The compounds of formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledons Cultures, both pre-emergence and post-emergence.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble Che powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, if necessary using surface-active agents, that is Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Lö be used as auxiliary solvents. Com as liquid solvent  essentially in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorine benzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as Cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvent solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fat alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. Lignin-Sul fitablaugen and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipi de, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.  

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides such as z. B. 1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or N- (2-benzothiazolyl) -N, N'- dimethyl urea for weed control in cereals; 4-amino-3-methyl-6-phenyl 1,2,4-triazin-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1- dimethylethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one for weed control in soy beans in question. Surprisingly, some mixtures also show synergistic effects Effect.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plant nutrients substances and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use solder solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, Scatter.

The active compounds according to the invention can be used both before and after emergence of the plants are applied.

They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. they depends essentially on the type of effect desired. Generally lie the application rates between 0.01 and 15 kg of active ingredient per hectare of soil, preferably between 0.05 and 10 kg per ha.  

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples Example 1 (Method (a))

2.34 g (15 mmol) chloroformic acid phenyl ester at 10 ° C to 20 ° C under Stir to a mixture of 3.53 g (15 mmol) of 2-ethoxycarbonyl-thiophene-3-sul fonamide, 3.03 g (30 mmol) of triethylamine and 60 ml of acetonitrile. After three The mixture is stirred for a minute for 1.44 g (15 mmol) of methane sulfonic acid and 2.10 g (15 mmol) of 2-amino-4-methoxy-6-methyl-s-triazine. The reaction mixture is heated under reflux for 30 minutes. Then in Water jet vacuum concentrated and the residue with water / methylene chloride shaken up. The organic phase is separated off and dried with sodium sulfate and filtered. The filtrate is concentrated, the residue is stirred with diethyl ether and the crystalline product is isolated by suction.

3.4 g (57% of theory) of N- (4-methoxy-6-methyl-s-triazin-2-yl) -N '- (2-eth oxycarbonyl-thien-3-yl-sulfonyl) urea with a melting point of 166 ° C.  

Example 2 (Method (b))

A mixture of 7.7 g (55 mmol) of 2-amino-4-methoxy-6-methyl-s-triazine, 14.4 g (55 mmol) 2-ethoxycarbonylthien-3-yl sulfonyl isocyanate and 100 ml acetonitrile is heated under reflux for 4 hours and then slowly cooled to 20 ° C. The the crystalline product is isolated by suction.

15.6 g (71% of theory) of N- (4-methoxy-6-methyl-s-triazin-2-yl) -N ′ - (2- ethoxycarbonyl-thien-3-yl-sulfonyl) urea with a melting point of 166 ° C.

Analogous to Examples 1 and 2 and in accordance with the general description the manufacturing method according to the invention can, for example, also that in Compounds of formula (I) listed below Table 1 who prepared the.

Table 1

Examples of the compounds of the formula (I)

The intermediates mentioned above as new compounds can be represented by the following formulas:
Formula (IX)

in which
A represents NH ₂ , NH-CO-OR ³ or N = C = O,
R ^{1 represents} ethyl or n-propyl and
R ^{3 represents} C ₁ -C ₄ alkyl, phenyl or benzyl,
represents the thiophene derivatives of the above formulas (II), (IV) and (VI).
The formula (X)

in which
E represents NH ₂ or SO ₂ Cl,
represents the thiophene derivatives of the formulas (VIII-1) and (VII-1).

Starting materials of formula (II) Example (II-1)

46 g of ammonia are stirred into a solution cooled to 0 ° C to 10 ° C 50 g (187 mmol) of 2-propoxycarbonyl-thiophene-3-sulfonic acid chloride in 500 ml Methylene chloride initiated. The reaction mixture is stirred at 20 ° C. for 15 hours and then filtered. The filtrate is concentrated, the residue is stirred with diethyl ether and the crystalline product isolated by suction.

31 g (67% of theory) of 2-propoxycarbonyl-thiophene-3-sulfonamide are obtained Melting point 79 ° C.

Example (II-2)

Analogously, 2-ethoxycarbonyl-thiophene-3-sulfonamide is also obtained from the melting point 136 ° C.

Starting materials of formula (VII) Example (VII-1)

A solution of 76 g (1.10 mol) of sodium nitrite in 140 ml of water is at -5 ° C to 0 ° C within 60 minutes to a solution of 185 g (1.00 mol) of 3-amino-thio phen-2-carboxylic acid propyl ester added dropwise in 630 ml of hydrochloric acid. The Ge Mix is stirred for 60 minutes at 0 ° C and then dropwise at 15 ° C to a Solution of 600 g sulfur dioxide in 1200 ml acetic acid, to which 115 ml of a saturated aqueous solution of copper (I) chloride. The reaction mixture is then stirred at 20 ° C. for 15 hours, then with ice water diluted to about twice the volume and extracted twice with methylene chloride. The combined organic extraction solutions are dried with sodium sulfate net and filtered. The solvent is carefully removed from the filtrate in a water jet vacuum distilled off.

205 g (76% of theory) of 2-propoxycarbonyl-thiophene-3-sulfonic acid are obtained chloride as an oily residue, which goes to the next reak without further purification tion level can be used.  

Example (VII-2)

Analogously, 2-ethoxycarbonyl-thiophene-3-sulfonic acid chloride is also obtained

Preparation of 3-amino-thiophene-2-carboxylic acid propyl ester: Example (VIII-1)

By reacting 2.6 g (113 mmol) sodium with propanol (100 ml) at 50 ° C a sodium propylate solution is prepared. To this solution at 20 ° C Solution of 6.7 g (50 mmol) of thioglycolic acid n-propyl ester in 20 ml of propanol drips and then at 25 ° C to 30 ° C (external cooling required) a solution of 4.4 g (50 mmol) of 2-chloro-acrylonitrile are metered into 20 ml of propanol. The reaction ge the mixture is stirred for 20 hours at 20 ° C., then concentrated to about 1/3 of the volume, then diluted with 100 ml of water and extracted three times with 100 ml of diethyl ether. The combined organic extraction solutions are washed with water, with Dried sodium sulfate and filtered. The solvent in the water is removed from the filtrate jet vacuum carefully distilled off.

5 g (54% of theory) of 3-amino-thiophene-2-carboxylic acid propyl ester are obtained as oily residue, which can be implemented directly.  

Examples of use

In the following application examples, the verb below is used used as a reference substance:

N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -N ′ - (2-methoxycarbonylthie-n-3-yl-sulfonyl) urea (thifensulfuron-methyl)
(known from EP-A 30 142).

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent, specifies the added amount of emulsifier and dilute the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after 24 hours with poured the active ingredient preparation. You keep the amount of water per Area unit expediently constant. The drug concentration in the Preparation is irrelevant, the only decisive factor is the amount of the active ingredient per unit area. After three weeks, the degree of damage to the plants rated in% damage compared to the development of the untreated control. It means:

0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 1 show 4, 9, 10, 12, 14, 16, 17, 19, 20, 21, 22 and 23 with sometimes very good tolerance to crops, such as. B. wheat, very strong action against weeds.  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent indicates that given amount of emulsifier and dilute the concentrate with water to the desired concentration.

Test plants are sprayed with the active ingredient preparation, which have a height of 5-15 cm so that the desired amounts of active ingredient per unit area be brought. The concentration of the spray liquor is chosen so that in 2000 l Water / ha the desired amounts of active ingredient are applied. After three The degree of damage to the plants is rated in% damage in weeks Comparison to the development of the untreated control. It means:

0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 1 show 3, 4, 5, 9, 10, 12, 13, 14, 17, 19, 20, 21, 22 and 23 with consistently very good Compatibility with crops, such as. B. wheat, very strong effect against weeds.

Claims (10)

1. Substituted thienylsulfonylureas of the general formula (I) in which
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X and Y are the same or different and each represents hydrogen, hydroxy, amino, cyano, halogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ - haloalkyl, C ₁ -C ₄ - alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - haloalkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylamino or di (C ₁ -C ₄ alkyl) amino and
Z represents nitrogen, a CH group or a C-halogen group,
and salts of compounds of formula (I). 2. Compounds of formula (I) according to claim 1, characterized in that therein
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X for hydrogen, hydroxy, amino, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, trifluoromethyl, methoxymethyl, ethoxymethyl, methoxyethyl , Ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, chloroethoxy, fluoroethoxy, dichloroethoxy, difluoroethoxy, trichloroethoxy, trifluoroethoxy, chlorodifluoroethoxy, methoxyethoxy, ethoxyethoxy, methylithio, methylethyl or ethylthio, ethyl-, ethyl- , n- or i-propylamino, dimethylamino or diethylamino,
Y represents hydrogen, hydroxy, amino, cyano, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino and
Z represents nitrogen or a CH group. 3. Compounds of formula (I) according to claim 1, characterized in that therein
R ^{1 represents} ethyl or n-propyl,
R ^{2 represents} hydrogen or methyl,
X represents methyl, methoxy or methylthio,
Y represents hydrogen, methyl, methoxy or methylthio and
Z represents nitrogen or a CH group. 4. A process for the preparation of substituted thienylsulfonylureas of the formula (I) according to claim 1, characterized in that

• a) thiophene sulfonamides of the general formula (II) in which
  R ^{1 has} the meaning given in claim 1,
  with chloroformic acid esters of the general formula (III) CI-CO-O-R³ (III) in which
  R ^{3 represents} C ₁ -C ₄ alkyl, phenyl or benzyl,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and the urethanes (carbamates) of the general formula (IV) formed in which
  R ¹ and R ^{3 have} the meaning given in claim 1, - optionally without intermediate insulation -
  with azines of the general formula (V) in which
  R ² , X, Y and Z have the meaning given in claim 1,
  if appropriate in the presence of a reaction auxiliary, or that
• b) thienylsulfonyl isocyanates of the general formula (VI) in which
  R ^{1 has} the meaning given above,
  with azines of the general formula (V) in which
  R ² , X, Y and Z have the meaning given above, optionally in the presence of a diluent.

5. Herbicidal agents, characterized by a content of at least one A compound of formula (I) according to claim 1. 6. Use of compounds of general formula (I) according to claim 1 to combat unwanted plant growth. 7. A method of combating weeds, characterized in that Compounds of general formula (I) according to claim 1 on the weeds or let their living space take effect. 8. A process for the preparation of herbicidal compositions, characterized in that compounds of the general formula (I) according to claim 1 with stretch agents and / or surface-active agents mixed. 9. Thiophene derivatives of the formula (IX) in which
A represents NH ₂ , NH-CO-OR ³ or N = C = O,
R ^{1 represents} ethyl or n-propyl and
R ^{3 represents} C ₁ -C ₄ alkyl, phenyl or benzyl. 10. Thiophene derivatives of the formula (X) in which
E represents NH ₂ or SO ₂ Cl.